JPH06172763A - Gasoline composition - Google Patents

Abstract

(57) [Summary] [Structure] A monoethylenic unsaturated group in which the ratio of the dicarboxylic acid moiety to the polyalkenyl chain is 1.2 or less, and the number average molecular weight (M _n ) of the polyalkenyl chain is 1600 to 5000. C ₄ -C ₁₀ polyalkenyl derivatives of dicarboxylic acids material is reacted with at least one amine obtained, gasoline compositions and gasoline additive concentrates containing an effective additive to reduce the deposit of the intake valve I will provide a. [Effect] The intake valve deposit is reduced.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to gasoline compositions and gasoline additive concentrates for use in internal combustion engines.

[0002]

It is known that during operation of an internal combustion engine the required octane number (OR), ie the fuel octane number required for knock-free operation, gradually increases with the accumulation of deposits in the combustion chamber.

Hydrocarbon fuels are used to prevent or suppress the formation of deposits or to remove or reform the deposits formed in the combustion chamber and adjacent surfaces (eg, valves, ports and spark plugs) to lower octane number requirements. Many additives that can be added are known. Such additives may typically include amines, polyamines, alkanols or polyols attached to long chain hydrocarbon polymers (eg polyisobutylene) via acid groups (eg dicarboxylic acid groups such as succinic acid groups). For example, it is possible to add succinimide substituted with a polyolefin of tetraethylenepentamine to a gasoline composition to suppress deposit formation in the fuel intake system of an internal combustion engine.
It is known as 960,493. The disclosed succinimides have the general formula:

[0004]

[Chemical 1]

Where R is derived from a polymer RH of an olefin containing 2 to 5 carbon atoms, the polymer being 30
Containing ~ 200 carbon atoms). Group R
Has a molecular weight of 400 to 3000, more preferably 900 to
1200, preferably derived from an isobutene polymer having a molecular weight of about 1000. In practice, the only example polyolefin of succinimide substituted with a tetraethylenepentamine polyolefin has a molecular weight of about 10
00 is polyisobutylene.

US Pat. No. 3,443,918 contains a major portion of liquid hydrocarbons boiling in the boiling range of gasoline, and the alkenyl group of the succinate moiety is about 50-25.
Contains 0 carbon atoms (ie, a molecular weight of about 700-3,5
00), preferably a molecular weight of about 700-350
0, more preferably 800 to 3200 polyisobutenyl groups, the polyamine having the formula:

[0007]

[Chemical 2]

(Wherein R is a polymethylene group containing 4 to 9 carbon atoms, s is 2 to 3, t is 0 to 1, and the sum of s + t is 3). Disclosed is a fuel composition containing a bis or tris-polymethylene polyamine mono- or bis-alkenyl succinimide in an amount sufficient to inhibit deposit formation. The only succinimide compound illustrated is a monoalkenyl succinimide in which the alkenyl group is a polyisobutylene group with an average molecular weight of 1000.

DE-OLS-3,126,404 is
In the first stage, at least one unsaturated anhydride (eg maleic anhydride), at least 10, preferably 20
Reacting with at least one olefin containing ~ 200 carbon atoms (i.e. having a molecular weight of at least 140, preferably 280-2800) and quenching as soon as at least 20% and up to 80% of the anhydride has reacted. Let
In the second stage, the product obtained in the first stage is represented by the general formula:

[0010]

[Chemical 3]

(R 'is a monovalent aliphatic group containing 6 to 30 carbon atoms, n is an integer of 2 to 5, and m is 1 to 1).
Disclosed is a gasoline composition comprising a detersive nitrogen composition produced by reacting with a polyamine represented by the formula: The only olefins used in the examples are polyisobutylene with a molecular weight of 920 and a molecular weight of 16
8 is tetrapropylene.

GB-A-960,493, US-A-
3,443,918 and DE-OLS-3,126,
None of 404 discloses steps to achieve a particular ratio of dicarboxylic acid moieties to polyolefin chains.

EP-A-208,506 contains C ₂ having a fuel or lubricating oil and a molecular weight of 1500-5000.
-C ₁₀ monoolefins olefin polymer (e.g., polyisobutylene: PIB) and C ₄ -C ₁₀ monounsaturated acid material (e.g. maleic anhydride: MALA) and C ₄ -C hydrocarbyl substituted that is generated by reacting the ₁₀ An amine derivative of an oily additive containing a monounsaturated dicarboxylic acid-forming material is contained as an ashless dispersant, and the average number of dicarboxylic acid-forming moieties per olefin polymer molecule used in the reaction is 1.05 to 1.25. An oily composition is disclosed. Examples 1-1 of EP-A-208,560
All 1 describe the production and testing of the lubricating oil composition only.

It will be apparent to those skilled in the art that it is practically impossible to completely react all polyolefins (eg PIB) with maleic anhydride (MALA).
In this case, the MALA / PIB of the actual chemicals produced
The ratio is higher than if calculated on the basis of all the polyolefins originally present in the reaction mixture. Therefore, when 80% of the polyolefin was incorporated into the product (which is a practical result of the process), MALA based on all the polyolefin reactants originally present.
If the / PIB ratio is 1.05 to 1.25, the product molecule ratio is actually about 1.3 to 1.5.

[0015]

Surprisingly, in particular, polyalkenyl derivatives of dicarboxylic acids and amines having relatively high polyalkenyl moieties (M _n ) and a low ratio of dicarboxylic acid moieties to polyalkenyl chains are disclosed. It has been found that the addition of certain additives, obtained by reacting ## STR3 ## to a gasoline composition, is particularly effective in reducing intake valve deposits.

[0016]

Accordingly, in accordance with the present invention, the ratio of dicarboxylic acid moieties to polyalkenyl chains is 1.
Reacting a polyalkenyl derivative of a monoethylenically unsaturated C ₄ -C ₁₀ dicarboxylic acid material in which the number average molecular weight (M _n ) of the polyalkenyl chain is 1 or less and the number is 2 or less and at least one amine. A gasoline composition containing a small amount of the additive thus obtained and a large amount of gasoline is provided.

The amines used in the present invention preferably contain 1-8 nitrogen atoms C ₁ -C _30, more preferably C ₁
-C _18, is especially amine of C ₈ -C _12. Such amines include branched or unbranched saturated aliphatic primary or secondary amines containing 1 to 8 nitrogens, preferably monoamines or diamines (eg ethylamine, butylamine, s
ec-butylamine, diethylamine and 3-dimethylamino-1-propylamine), but with the nitrogen atom pair bound by an alkylene group containing from 2 to 4 carbon atoms (eg alkylenepolyamine).
Is included. Therefore, the _{formula: NH 2 (CH 2) m} - [NH (CH _{2) m] n} -NH ₂ (I) (wherein, m is 2 to 4, n is a is 0-6) is represented by Polyamines are included.

Examples of such polyamines are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, tripropylenetetramine and commercially available mixtures thereof (for example "Polyamine").
"H", "Polyamine 400" and "Pol
Yamine S ″) is included.

The polyalkenyl derivative of the monoethylenically unsaturated C ₄ -C ₁₀ dicarboxylic acid material is a known compound or can be produced by a method similar to the known method. Thus, for example, a polyalkene, as described in JP GB-A-949,981 was mixed with a specific amount of monoethylenically unsaturated C ₄ -C ₁₀ dicarboxylic acid material, for producing such derivatives through chlorine in the mixture Can be convenient. Alternatively, for example, as described in GB-A-1,483,729, a polyalkene and a specific amount of a dicarboxylic acid material may be thermally reacted at an appropriate temperature to produce a derivative. A particularly advantageous method of producing the derivative is to provide the polyalkene at a temperature of 150-260 ° C. in the presence of a polyaddition-inhibiting amount of sulfonic acid, with a molar ratio of dicarboxylic acid material to polyalkene being a number of 1 or greater: 1. It consists of reacting with a dicarboxylic acid material. Such a method is described in EP-A-542,380.
No.

The polyalkene is, for example, at least one C
Homopolymers or copolymers of ₂ -C ₁₀ monoolefins may be advantageous. Preferably the polyalkene at least one C ₂ -C ₅ monoolefin polymers such as ethylene - propylene copolymer. Monoolefin is preferably a C ₃ -C ₄ olefins, preferred polyalkenes derived therefrom include polyisobutylenes and atactic or isotactic propylene oligomers. Polyisobutylene (eg Briti
"Ul" from sh Petroleum Company
travis ”,“ Hyvis ”and“ Napvis ”
Products sold under the registered trademark of, for example, "Napv
is120 ”,“ Hyvis75 ”and“ Hyvis2 ”
00 "polyisobutylene is particularly preferred for use in the present invention.

The number average molecular weight (M _n ) of the polyalkene is
It may be measured by a number of known techniques that give substantially similar results. Therefore, M _{n is represented} by, for example, “Moden Siz
eExclusion Liquid Chromat
ography ”(WW Yau, JJ K
irkland and D.I. D. Bly, John Will
ey and Sons, New York, 19
79) new gel permeation chromatography (GPC), vapor phase osmometry (VPO) or assuming that each oligomer chain contains one double bond as described in the examples below. It may be measured by a quantitative reaction with ozone. This will be easily understood by those skilled in the art.

For example, "Topics in Chemi"
cal Instrumentation, Volume
e XXIX, Gel Permeation Chr
omatography ”(Jack Cases, T
he Journal of Chemical Edu
Cation, Volume 43, numbers
7 and 8, (1966)), especially U
If one applies the conventional GPC method as disclosed in S-A-4,234,435, the _Mn values obtained will probably be higher than those obtained with the method described above. For example, for materials with M _n greater than 2000, these conventional G
The values obtained by the PC method can be as much as 10 to 17% higher than the values obtained by the method described above.

The M _n of the polyalkene used in the present invention is from 1600 to 5000 according to the above-mentioned method, preferably at least 1700, more preferably at least 1.
800, most preferably at least 1850 to 4,000
0, more preferably 3,500, advantageously 3,0
00, most preferably 2,500.

C ₄ -C ₁₀ dicarboxylic acid materials (eg US
-A-4,086,251 and US-A-4,23
No. 5,786) can be, for example, the anhydrides of C ₄ -C ₆ dicarboxylic acids [eg maleic acid, citraconic acid (methyl maleic acid), itaconic acid (methylene succinic acid) and ethyl maleic acid]. C ₄ -C ₁₀ dicarboxylic acid material is preferably maleic anhydride.

When the C ₄ -C ₁₀ dicarboxylic acid material is maleic anhydride, the polyalkenyl derivative is a polyalkenyl succinic acid derivative.

The ratio of dicarboxylic acid moieties to polyalkenyl chains (referred to as the "amber oxidation rate" when the dicarboxylic acid material is maleic anhydride) is given by the formula:

[0027]

[Equation 1]

[Wherein M _n is the number average molecular weight of the polyalkene, AV is the acid value (meq / g) of the reaction product, AM is the active substance content (% by weight) of the reaction product, _{MD A} is simply the molecular weight of the dicarboxylic acid material (maleic anhydride is 98)].

The "active substance" is a monoethylenically unsaturated C
Means ₄ -C ₁₀ actual polyalkenyl derivatives of dicarboxylic acids material. From this, the unreacted polyalkene is A
It is considered that it does not contribute to M.

The ratio of dicarboxylic acid moieties to polyalkenyl chains is preferably 1: 1 to 1.2: 1, more preferably 1: 1 to 1.15: 1.

The manufacture of additives for use in the gasoline composition of the present invention is known in the art. Therefore, the molar ratio of polyalkenyl derivative / amine is usually 1 to 4, preferably 1.5 to 2.5, and at least one amine is a polyalkenyl of a monoethylenically unsaturated C ₄ -C ₁₀ dicarboxylic acid material. It is convenient to react with the derivative.

1-1 in an organic solvent at a temperature of 100 to 250 ° C., preferably 125 to 175 ° C., advantageously 160 ° C.
It is convenient to react for 0 hours and then strip with nitrogen at similar temperatures for about 1-5 hours. Preference is given to reacting in the absence of oxygen. Nitrogen blankets are often used to achieve this result.

Suitable organic solvents include hydrocarbons (eg hexane, cyclohexane, toluene, xylene) and mineral oils (eg Royal Dutch / Shell Gr).
"HVI" and "XHVI" from companies that are members of our
The products sold under the registered trademarks are included.

The amount of additive present in the gasoline composition of the present invention is preferably 10 to 1000 ppmw, more preferably 50 to 500 ppmw, especially 100 to 400 pp.
mw (all ppmw are based on the total composition).

The term "gasoline" refers to a liquid hydrocarbon fuel (basic fuel (basic fuel) which contains a mixture of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons, with gasoline boiling range 25-232 ° C. base fuel))
Means Preferably, the base fuel comprises 40-80% by volume saturated hydrocarbons, 0-30% by volume olefinic hydrocarbons and 10-60% by volume aromatic hydrocarbons. Base fuels are straight run gasoline, polymer gasoline, natural gasoline, trimer or dimerized olefins, hydrocarbons thermally or catalytically reformed or synthetic aromatic carbons obtained from catalytically or thermally cracked feedstocks. It can be derived from hydrogen mixtures, or mixtures thereof. The hydrocarbon composition and octane number of the base fuel are not important. The octane number ((R + M) / 2) is generally 85 or more. Conventional automotive base fuels may be used in the practice of the present invention. Thus, instead of the hydrocarbons in gasoline, alcohols, ethers, ketones or esters conventionally known for use in fuels can be used to a considerable extent. Of course, it is preferred that the base fuel be substantially free of water. This is because water can hinder smooth burning.

The gasoline composition of the present invention may further contain other additive components or additives. Thus, gasoline may include lead compounds as antiknock agents. Therefore, the gasoline composition of the present invention contains leaded gasoline and unleaded gasoline. The gasoline composition may further include an antioxidant (eg, 2,
Phenols such as 6-di-t-butylphenol,
N, N'-di-sec-butyl-phenylenediamines such as p-phenylenediamine), dyes, metal deactivators, dehazers (eg polyester type ethoxylated alkylphenol-formaldehyde resins), corrosion Inhibitors (eg polyhydric alcohol esters of succinic acid derivatives having an unsubstituted or substituted aliphatic hydrocarbon group having 20 to 500 carbon atoms on at least one α-carbon atom (eg number average molecular weight). Of succinic acid substituted with a polyisobutylene group of 950), and anti-knock agents other than lead compounds (for example, methylcyclopentadienyl-).
Manganese tricarbonyl or ortho-azidophenol), antiknock auxiliaries (eg benzoylacetone), or carrier fluids (eg C ₁₂ -C ₁₅ alkyl substituted polyethers such as propylene glycol (R
"SAP 949") sold by companies that are members of the Oyal Dutch / Shell group),
"HVI" base oil, "XHVI" base oil or 20 to 17
5, in particular include C ₂ -C ₆ polyolefins derived from monomers), such as polyisobutylene having 35 to 150 carbon atoms.

The additives may be added to the gasoline separately or may be blended with other additives and added to the gasoline. The preferred method of adding the additive to the gasoline is to first make the additive concentrate and then add the calculated amount of the concentrate to the gasoline.

Accordingly, the present invention provides a gasoline compatible diluent and a dicarboxylic acid moiety to polyalkenyl chain ratio of 1.
Reacting a polyalkenyl derivative of a monoethylenically unsaturated C ₄ -C ₁₀ dicarboxylic acid material in which the number average molecular weight (M _n ) of the polyalkenyl chain is 1 or less and the number is 2 or less and at least one amine. 20 obtained from
A gasoline additive concentrate comprising 50% by weight (calculated based on diluent) of additive.

Suitable gasoline-compatible diluents are hydrocarbons and mixtures of hydrocarbons with alcohols or ethers (for example methanol, ethanol, propanol, 2-butoxyethanol or methyl-t-butyl ether). Preferably the diluent is an aromatic hydrocarbon solvent such as toluene, xylene, a mixture of these two components or a mixture of toluene or xylene with an alcohol.

[0040]

The invention will be better understood by the following examples. The number average molecular weight (M _n ) of the polyisobutylene used was measured by quantitative reaction with ozone, assuming that each oligomer chain contains one double bond, unless otherwise stated. This will be easily understood by those skilled in the art.

The active material content was determined by separating the inactive material from the desired active material using an aluminum oxide column using diethyl ether as the eluent. The acid value was measured according to ASTM D664.

Example 1 (i) Preparation of a polyisobutenyl derivative of maleic anhydride As described in GB-A-949,981, "Hyvis 75" (R) polyisobutylene having a number average molecular weight ( _Mn ) of 1890. (PIB) is reacted with maleic anhydride to give an active substance content of 73.0% by weight and an acid value of 0.
84 meq / g of PIB-MALA reactant was obtained. This analysis data is based on the amber oxidation rate (MAL
The number of moles A / the number of moles of PIB) is 1.15.

(Ii) PIB-MALA and polyamine
The reaction product of PIB-MALA obtained in (i) above was prepared by a conventional method using polyamine: tetraethylenepentamine (TE).
PA). Therefore, TEPA is replaced with PIB-MA
Add to LA at 160 ° C over 1.5 hours (PIB-MA
The LA / TEPA molar ratio is 1.5) and the material in the reactor is maintained at this temperature for an additional hour and then stripped with nitrogen to remove all water of reaction to give the desired final product (succinimide). ) Got. TE added to PIB-MALA
The amount of PA was 52.9 g / kg of PIB-MALA. This quantity has the following formula:

[0044]

[Equation 2]

(In the formula, Io is the number of g of polyamine added to 1 kg of PIB-MALA, Ma is the molecular weight of polyamine (TEPA is 189), and Ao is PIB.
-MALA acid number, CR is PIB-MALA / polyamine molar ratio).

[0046] changing the amount and type of Examples 2-4 and Comparative Examples A~D reagents used were Examples 2-4 and Comparative Examples A~D carried out in the same manner as in Example 1. However, Example 2
Then, step (i) is carried out in the same manner as in Examples 1 to 8 of EP-A-542,380, and in Example 4 and Comparative Examples A and B, GB-A-1,483,729. Step (i) was carried out as described in 1. Polyamine used, C
R value, polyisobutylene type and M _n used in Examples 2 to 4 and Comparative Examples A to D, and active substance content and acid value of PIB-MALA reactant which is an intermediate obtained in these examples. And the amber oxidation rate is shown in Table I below. The following abbreviations are used in the table.

TETA: triethylenetetramine TEPA: tetraethylenepentamine Polyamine S: mixture of tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine (molar ratio 1: 2: 1)

[0048]

[Table 1]

* Comparative examples A and B are _{Mn of} PIB.
Is a comparative example not within the range of 1600 to 5000.

** Comparative Examples C and D are Comparative Examples in which the amber oxidation rate exceeds 1.2.

Example 5 Each of the final products (succinimide) obtained in Examples 1 to 3 and Comparative Examples A to D was subjected to Vo for the cleanability of the intake valve.
lkswagen (VW) Polo RoadTest
Tested in. Active succinimide 8 based on the total composition
0 ppmw and (i) "HVI" base oil as a carrier fluid, that is, "HVI 60" base oil [viscosity at 100 ° C. is 4.4 to 4.9 mm ² / sec (ASTM D445), flash point is 204 ° C. (ASTM D93), pour point is -15
~-18 ℃ (ASTM D97) and a high base oil transparent and viscosity index] "HVI 160" viscosity base oil [100 ° C. is 10.7~11.8mm ² / s (ASTM D44
5), 200 ppmw of a 1: 1 mixture with a transparent base oil having a flash point of 228 ° C (ASTM D93) and a pour point of -9 ° C (ASTM D97) and a high viscosity index, or (ii).
It was prepared by using a mixture of C ₁₂ -C ₁₅ alcohols as an initiator, has an M _n of 1200 to 1500, a kinematic viscosity at 40 ° C. of 72 to 82 mm ² / sec (ASTM D445), and a Royal Dutch / Shell group.
A test was carried out using unleaded gasoline containing 250 ppmw of polyoxypropylene glycol hemiether (monoether) sold under the trade name "SAP949" by a company affiliated with.

In this test, a standard car of VW company equipped with an engine with a displacement of 1043 cc equipped with a carburetor and a small wind vane mounted on the roof in order to increase the wind resistance and thereby the load of the car was tested. The gasoline composition was used to run for 5000 km. Before starting the test, the deposit was removed from the cylinder head, intake manifold, piston head and combustion chamber and a new intake valve was weighed and installed. Replace the oil and filter,
Installed a new spark plug. A 37 minute test cycle was used. The test was 4500 rpm with the vehicle in 4th speed.
It consisted of running for 30 minutes at (65 mph or 104.6 km / hour) and then for 7 minutes at idle. A total of 12 cycles were performed in one day, and then a stop period was set, which was repeated every day for a total of 8 days (see Table I below).
I)).

[0053]

[Table 2]

Test time = 60 hours Test cycle number = 96 times Test distance = 5000 km.

After the test was completed, the intake valve was removed and the weight was measured. Tables III and IV below show the average weight of four intake valve deposits for each test composition.

[0056]

[Table 3]

[0057]

[Table 4]

The gasoline composition of the present invention has a significantly smaller amount of deposit than the gasoline composition of Comparative Example,
It can therefore be apparent from the test results in Tables III and IV above that the engine performance is significantly improved.

Example 6 In this example, 300 pp of a 40% w / w xylene solution in which the final product of Example 4 (succinimide) (120 ppmw active substance) is dissolved, based on the total composition.
mw and carrier fluid "SAP949" hemiether 300p
Unleaded gasoline containing pmw and Vo as described in Example 5
lkswagen (VW) Polo Road Tes
Tested at t. The results obtained are shown in Table V below.

[0060]

[Table 5]

The test results in Table V show that excellent engine performance is obtained with the gasoline composition containing the succinimide of Example 4, which is a composition of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jio Diff Graham United Kingdom, Merseyside El 63.0 N E, Wirral, Lavie Mia, Mia Avenyu, 17

Claims (10)

[Claims] 1. A monoethylenically unsaturated C ₄ -C in which the ratio of the dicarboxylic acid moiety to the polyalkenyl chain is 1.2 or less and the number is 1 and the number average molecular weight (M _n ) of the polyalkenyl chain is 1600 to 5000. ₁₀ A gasoline composition containing a small amount of an additive obtained by reacting a polyalkenyl derivative of a dicarboxylic acid material with at least one amine, and a large amount of gasoline. 2. The gasoline composition of claim 1, wherein the ratio of dicarboxylic acid moieties to polyalkenyl chains is 1: 1 to 1.15: 1. 3. A polyalkenyl chain having an M _n of 1700 to 3
The gasoline composition according to claim 1 or 2, wherein the gasoline composition is 500. 4. The M _n of the polyalkenyl chain is 1800-2.
The gasoline composition according to any one of claims 1 to 3, wherein the gasoline composition is 500. 5. The polyalkenyl chain comprises at least one C
₂ -C ₅ gasoline composition according to any one of claims 1, characterized in that it is derived from the polymers of monoolefins 4. 6. The gasoline composition according to claim 5, wherein the monoolefin is isobutylene. 7. The amine has the general formula: NH ₂ (CH ₂ ) _m — [NH (CH ₂ ) _m ] _n —NH ₂ (I) (wherein m is 2 to 4 and n is 0 to 6). The gasoline composition according to any one of claims 1 to 6, which is a compound represented by the formula (1). 8. The amount of additive is 10 to 10 based on the total composition.
It is 1000 ppmw, The gasoline composition as described in any one of Claim 1 to 7 characterized by the above-mentioned. 9. The amount of additive is from 50 to 50, based on the total composition.
It is 500 ppmw, It is characterized by the above-mentioned.
The gasoline composition according to any one of 1. 10. A gasoline compatible diluent with a number of dicarboxylic acid moieties to polyalkenyl chains of 1.2 or less: 1
And the number average molecular weight (M _n ) of the polyalkenyl chain is 160
Addition of 20 to 50% by weight (calculated based on diluent) obtained by reacting 0 to 5000 polyalkenyl derivative of monoethylenically unsaturated C ₄ -C ₁₀ dicarboxylic acid material with at least one amine. A gasoline additive concentrate containing an agent.